WO2022211141A1 - Composition de revêtement de balai d'essuie-glace comprenant du graphène fonctionnalisé ayant une adhésivité améliorée au caoutchouc, et son procédé de préparation - Google Patents

Composition de revêtement de balai d'essuie-glace comprenant du graphène fonctionnalisé ayant une adhésivité améliorée au caoutchouc, et son procédé de préparation Download PDF

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WO2022211141A1
WO2022211141A1 PCT/KR2021/003893 KR2021003893W WO2022211141A1 WO 2022211141 A1 WO2022211141 A1 WO 2022211141A1 KR 2021003893 W KR2021003893 W KR 2021003893W WO 2022211141 A1 WO2022211141 A1 WO 2022211141A1
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group
functionalized graphene
wiper blade
functional group
coating composition
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PCT/KR2021/003893
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English (en)
Korean (ko)
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김명기
진성민
홍성민
오지택
김정훈
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베스트그래핀(주)
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Priority to KR1020237023571A priority Critical patent/KR20230121804A/ko
Priority to US18/270,834 priority patent/US20240075905A1/en
Priority to PCT/KR2021/003893 priority patent/WO2022211141A1/fr
Publication of WO2022211141A1 publication Critical patent/WO2022211141A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60S—SERVICING, CLEANING, REPAIRING, SUPPORTING, LIFTING, OR MANOEUVRING OF VEHICLES, NOT OTHERWISE PROVIDED FOR
    • B60S1/00—Cleaning of vehicles
    • B60S1/02—Cleaning windscreens, windows or optical devices
    • B60S1/04—Wipers or the like, e.g. scrapers
    • B60S1/32—Wipers or the like, e.g. scrapers characterised by constructional features of wiper blade arms or blades
    • B60S1/38—Wiper blades
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60S—SERVICING, CLEANING, REPAIRING, SUPPORTING, LIFTING, OR MANOEUVRING OF VEHICLES, NOT OTHERWISE PROVIDED FOR
    • B60S1/00—Cleaning of vehicles
    • B60S1/02—Cleaning windscreens, windows or optical devices
    • B60S1/04—Wipers or the like, e.g. scrapers
    • B60S1/32—Wipers or the like, e.g. scrapers characterised by constructional features of wiper blade arms or blades
    • B60S1/38—Wiper blades
    • B60S2001/3827—Wiper blades characterised by the squeegee or blade rubber or wiping element
    • B60S2001/3829—Wiper blades characterised by the squeegee or blade rubber or wiping element characterised by the material of the squeegee or coating thereof

Definitions

  • the present invention relates to a wiper blade coating composition comprising functionalized graphene with improved adhesion to rubber and a method for manufacturing the same.
  • the wiper currently used in automobiles has a wiper blade rubber material combined with a wiper arm.
  • the wiper rotates while the wiper blade rubber base is in close contact with the windshield to remove snow, rain, or foreign substances to secure visibility. Since the wiper blade rubber base moves in close contact with the windshield, it is necessary to lower the friction force of the wiper blade rubber base against the windshield. If the friction force of the wiper blade rubber material on the windshield is too high, not only noise is generated during the operation of the wiper, but also the wiper vibrates and does not properly remove snow, rain or foreign substances.
  • the surface of the wiper blade rubber material formed of a material such as natural rubber and chlorinated rubber is surface-treated or an additive is used.
  • the surface treatment method is to reduce the friction coefficient of the wiper blade rubber material by halogenating the surface of the wiper blade rubber material.
  • the surface of the halogenated rubber base hardens over time, and when it hardens, it does not adhere well to the glass window, so the ability to remove snow, rain, or foreign substances is significantly reduced, and furthermore, noise and vibration are more severe.
  • the method of using the additive is to realize a uniform coefficient of friction for the rubber-based glass by using an additive composed of fluorine-based resin, silicone rubber powder, and silicone resin. Although this method is effective in preventing noise and vibration in the beginning, there is a problem in that durability is rapidly reduced when used for a long period of time.
  • the method of using the surface treatment or additives for the polymer blade rubber substrate has the above problems, and recently, a method of forming a coating layer on the surface of the rubber substrate using a coating solution has been proposed.
  • the method of forming the coating layer is to form a coating layer on the surface of the blade rubber base with a coating composition containing graphite, non-oxidized graphene, and the like.
  • the formed coating layer functions as a lubricating layer that reduces the coefficient of friction with respect to the glass, thereby reducing noise and vibration.
  • lubricating additives such as graphite and non-oxidized graphene, which give the coating layer a lubricating function, and rubber and different materials.
  • the amount of the binder of the coating composition is increased to compensate for the low adhesion of the lubricating additive to the rubber and the wiping durability performance, the ratio of the lubricating additive is reduced, thereby lowering the wiping performance.
  • One object of the present invention is to provide a coating composition for forming a coating layer with functionalized graphene capable of self-adhesion to a rubber substrate and a method for manufacturing the same.
  • a coating composition for a wiper blade according to another embodiment of the present invention for solving the above-described problems is a coating composition for forming a coating layer for lowering the friction coefficient of the wiper blade rubber-based glass with respect to the glass, and includes a lubricating additive and a solvent And, the lubricating additive is characterized in that the functionalized graphene capable of self-adhesion to the wiper blade rubber base.
  • the coating composition may be characterized in that it does not include a binder.
  • the content of the functionalized graphene may be characterized in that 0.1 to 1.0 wt%.
  • the functionalized graphene has a functional group A capable of self-attaching to the wiper blade rubber substrate, and the functional group A is an amine group, a silane group, an amide group, At least one selected from the group consisting of an azide group, a urea group, a urethane group, an alkylene group, an epoxide group, an anhydride, and a mercapto group It can be characterized as one.
  • the functionalized graphene includes an organic single molecule or polymer bonded to the functional group A, and the organic single molecule or polymer has a functional group B capable of self-attaching to the wiper blade rubber base, and the functional group B is an amine group, a silane group, an amide group, an azide group, a urea group, a urethane group, an alkylene group, and an epoxide group.
  • anhydride anhydride
  • it may be characterized in that at least one selected from the group consisting of a mercapto group (mercaptor).
  • the content ratio of the organic monomolecular or polymer to the functionalized graphene having the functional group A may be characterized in that 0.05 to 3.0.
  • the XRD 2 ⁇ degree of the functionalized graphene is 24.7 to 11.046°.
  • a method of manufacturing a coating composition for a wiper blade for solving the problems described above, the method comprising: (a) preparing an aqueous solution of graphene oxide; (b) preparing a first solution in which a first additive for forming a functional group A is dissolved in a first solvent; (c) preparing functionalized graphene having a functional group A by mixing the graphene oxide aqueous solution with the first solution and reacting by stirring; (d) separating the functionalized graphene on which the functional group A is formed through centrifugation, washing and drying; and (e) preparing a functionalized graphene colloid by placing the dried functionalized graphene formed thereon into a main solvent and performing ultrasonic dispersion.
  • step (f) mixing and ultrasonically dispersing the functionalized graphene colloid with a second solution in which the second additive is dissolved in a second solvent;
  • the second additive may be an organic monomolecular or polymer including a functional group B, and in step (f), the organic monomolecular or polymer may be combined with the functional group A.
  • the wiper blade coating composition of the present invention uses functionalized graphene having a self-adhesive functional group as a lubricant additive in the wiper blade coating composition. Since functionalized graphene can be self-adhesive to the wiper blade rubber base, the amount of binder included in the coating composition can be minimized or completely eliminated. That is, when the coating layer is formed on the rubber substrate of the wiper blade using the functionalized graphene of the present invention, it is possible to achieve both high wiping performance and high durability wiping performance of the wiper.
  • FIG. 2 is a schematic diagram of functionalized graphene according to the second embodiment.
  • FIG. 4 is a schematic cross-sectional view of a wiper with a coating layer formed of functionalized graphene of the present invention.
  • FIG. 5 is a schematic flowchart of a method for preparing the graphene composition of the present invention.
  • FIG. Figure 8 (a) is an image taken with an optical microscope of the surface of the wiper blade rubber base without a coating layer
  • FIG. Figure 8 (c) is an image taken with an optical microscope of the surface of the wiper blade rubber substrate formed of the coating layer of the embodiment.
  • the wiper blade In order to improve the adhesion to the windshield, the wiper blade is formed with a rubber base on the part in contact with the windowpane.
  • Graphite or MoS 2 which are conventionally used as lubricating additives in the coating composition for wiper blades, has a problem in that the durable wiping performance of the wiper is low because the lubricating performance does not have adhesion to rubber. The wiper continues during operation and the windshield and the wiper blade rub against each other. During the friction process, graphite or MoS 2 is separated from the surface of the rubber base of the wiper blade.
  • the wiper blade coating composition according to an embodiment of the present invention uses functionalized graphene to solve the problems of the prior art.
  • FIG. 1 is a schematic diagram of functionalized graphene of a first embodiment
  • FIG. 2 is a schematic diagram of functionalized graphene of a second embodiment.
  • the functionalized graphene of the first embodiment has a functional group A capable of self-attaching to rubber
  • the functionalized graphene of the second embodiment is an organic group having a functional group B capable of self-attaching to the rubber via the functional group A.
  • Monomolecules or polymers are bound.
  • the functional group A and the functional group B mean different functional groups.
  • the rubber base of the wiper blade may be any one selected from the group consisting of NR (natural rubber), SBR (Styrene Butadiene Rubber), NBR (Nitrile-butadiene rubber), EPDM (Ethylene Propylene Diene Monomer Rubber), and silicone rubber.
  • the functionalized graphene used in the present invention has the effect of being able to self-attach to the rubber substrate by the functional group A or the functional group B, and at the same time improving the dispersibility by the functional group A or the functional group B.
  • the functional group A is an amine group, a silane group, an amide group, an azide group, a urea group, a urethane group, and an alkylene group.
  • an epoxide group epoxide
  • anhydride anhydride
  • the functional group A is an amine group, a silane group, an amide group, an azide group, a urea group, a urethane group, and an alkylene group.
  • an epoxide group (epoxide), anhydride (anhydride) may be at least one selected from the group consisting of a mercapto group (mercaptor)
  • the functional group B is an amine group (amine), a silane group (silane), an amide group (amide), azide group (azide), urea group (urea), urethane group (urethane), alkylene group (alkylene), epoxide group (epoxide), anhydride (anhydride), from the group consisting of a mercapto group (mercaptor) It may be at least any one selected.
  • the functional group A and the functional group B have different molecular structures, and an organic single molecule or polymer having the functional group B is bonded to the functional group
  • Organic monomolecules or polymers having an amine group are ethylenediamine, triethylamine, paraphenylenediamine, 3,3',4,4'-tetraaminobiphenyl (3,3', 4,4'-tetraaminobiphenyl), 3,3',4,4'-tetraaminoterphenyl (3,3',4,4'-tetraaminoterphenyl), benzidine, 1,5-diaminonaphthalene (1 ,5-diaminonaphthalene), (E)-4,4'-(diazene-1,2-diyl)dianiline ((E)-4,4'- (diazene-1,2-diyl)dianiline), ethylene Diamine (Ethylenediamine), 1,6-diaminohexane (1,6-Diaminohexane), 1,8-diaminooctane (1,8-Diaminooactne), 4-amino
  • organic monomolecules or polymers having a silane group examples include polydimethylsiloxane (PDMS), tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), normal triethoxysilane, dimethyl silicone oil, methylphenylsiloxane.
  • PDMS polydimethylsiloxane
  • TMOS tetramethoxysilane
  • TEOS tetraethoxysilane
  • normal triethoxysilane dimethyl silicone oil
  • methylphenylsiloxane methylphenylsiloxane
  • any one selected from the group consisting of Polyamide 6, Polyamide 66, Polyamide 610, Polyamide 12, Polyamide 46, and Polyamide 4 may be used as a polymer linked by -CONH-, which is an amide bond.
  • the present invention is not limited thereto.
  • organic monomolecules or polymers having an azide group examples include Sodiumazide, 2-azidoethanol, 3-azidopropan-1-amine, 4-(2-azidoethoxy)-4-oxobutanoic acid, and 2-azido Any one selected from the group consisting of ethyl-2-bromo-2-methylpropanoate, chlorocarbonate, azidocarbonate, dichlorocarbene, carbene, arine and nitrene may be used, but the present invention is limited thereto it's not going to be Polyurea may be used as the organic monomer or polymer having a urea group, and polyurethane may be used as the organic monomer or polymer having a urethane group, and an organic monomer or polymer having an alkylene group may be used.
  • Polyurea may be used as the organic monomer or polymer having a urea group
  • polyurethane may be used as the organic monomer or polymer having a urethane group
  • any one selected from the group consisting of organic monomolecules or polymers having a carbon-carbon double bond may be used, but the present invention is not limited thereto.
  • organic monomolecules or polymers having an epoxide group include BPA, BPF, BP, Novolac (EOCN, OCN, etc.) type epoxy resins, ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, and octene oxide.
  • decene oxide decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, octadecene oxide, butadiene monoxide, 1,2-epoxide-7-octene, epifluorohydrin, epichlorohydrin, epibromohi drine, isopropyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, Cyclododecene oxide, alpha-pinene oxide, 2,3-epoxide norbornene, limonene oxide, dieldrin, 2,3-epoxidepropylbenzene, styrene oxide, phen
  • any one selected from the group consisting of acetic anhydride, benzoic anhydride, and maleic anhydride may be used as the organic monomer or polymer having an anhydride, but the present invention is not limited thereto.
  • organic monomolecules or polymers having a mercapto group include 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole (2,5-Dimercapto-). Any one selected from the group consisting of 1,3,4-thiadizole) and 2-mercaptobenzothiazole (2-Mercaptobenzothiazole) may be used, but the present invention is not limited thereto.
  • the functionalized graphene of the first or second embodiment of the present invention has an interplanar distance of 0.36 nm to 0.8 nm.
  • Graphite or non-functionalized conventional graphene has an interplanar distance of 0.335 nm, and in the case of graphene oxide, it is on the order of 0.85 to 1.25 nm.
  • the interplanar distance of functionalized graphene becomes 0.36 nm to 0.8 nm.
  • the interplanar distance of functionalized graphene is 0.35 nm or less, it means that there is no functional group capable of self-adhesion to the rubber substrate. this is lowered
  • FIG. 4 is a schematic cross-sectional view of a wiper with a coating layer formed of functionalized graphene of the present invention.
  • the wiper 100 of the present invention includes a wiper blade rubber base 10 and a coating layer 20 formed on the surface thereof.
  • the coating layer 20 serves as a lubricating additive to lower the friction coefficient between the wiper blade rubber base 10 and the glass window.
  • the coating layer 20 includes the functionalized graphene of the first embodiment or the functionalized graphene of the second embodiment described above.
  • the coating layer 20 is formed by the coating composition for a wiper blade of the present invention to be described later, and the binder may be very little (0.3 wt% or less) or no binder in the coating composition for a wiper blade of the present invention, and the solvent forms the coating layer. It evaporates and disappears in the process.
  • the coating layer 20 is formed only of the functionalized graphene of the present invention, or is composed of the functionalized graphene and a small amount of the binder residue.
  • the coating layer formed on the surface of the rubber base of the wiper of the present invention has a very high content of functionalized graphene that performs a lubricating function without using or minimizing the amount of binder because functionalized graphene has excellent adhesion to rubber. The durability of wiping performance is significantly improved.
  • the coating layer formed on the surface of the rubber base of the wiper of the present invention may be formed by a coating composition for a wiper blade.
  • the coating composition of the present invention includes a lubricating additive and a solvent, and the lubricating additive is characterized in that it is functionalized graphene capable of self-adhesion to the wiper blade rubber base.
  • the functionalized graphene may be any one of the functionalized graphene of the first embodiment and the functionalized graphene of the second embodiment described above, or a mixture thereof.
  • the content of functionalized graphene may be 0.1 to 1.0 wt.%.
  • Table 1 shows the results of measuring coating properties, adhesion, friction coefficient of wiper blades, initial wiping performance, and durable wiping performance (100,000 times) according to the content of functionalized graphene having an amine functional group as functional group A.
  • the content ratio of organic monomolecules or polymers to the functionalized graphene including the functional group A may be 0.05 to 3. Below 0.05, the amount of organic monomolecules or polymers is small, so there is hardly any improvement in adhesion. If it exceeds 3, the adhesion is very high, but the friction coefficient increases due to deterioration in lubrication performance, resulting in chattering between wiper operations (irregular vibration due to high friction between wiper operations). and noise generation) occurs, and durability is significantly reduced.
  • Table 2 evaluates the properties of the polymer (polyurethane) having a functional group B with respect to the functionalized graphene having a functional group A (amine group) by content.
  • the content ratio of organic monomolecules or polymers to the functionalized graphene including functional group A is 0.05 to 3, the adhesion is maximized, and the durable wiping performance is improved.
  • the content ratio of organic monomolecules or polymers to the functionalized graphene containing the functional group A exceeds 3.0, the adhesion is very good, but the lubricity is insufficient, so the frictional force increases, and at the same time, the wiping performance deteriorates, making it impossible to use due to chattering. There is a problem with termination.
  • the solvent only the main solvent may be used, or a sub-solvent may be used together with the main solvent for the purpose of controlling coating properties and drying process.
  • the main solvent may be any one selected from distilled water (DI water), ethanol (Ethanol), isopropyl alcohol (Isopropyl alcohol), the content may be 93.5 ⁇ 98.9 wt.%.
  • the cosolvent may be at least one selected from toluene, methyl ethyl ketone (MEK), dimethylacetamide (DMAc), butyl cellosolve (BC), and butyl cellosolve acetate (BCA), and the content thereof is 5 wt.% or less. .
  • MEK methyl ethyl ketone
  • DMAc dimethylacetamide
  • BC butyl cellosolve
  • BCA butyl cellosolve acetate
  • FIG. 5 is a schematic flowchart of a method for preparing the graphene composition of the present invention. A method for preparing the graphene composition of the present invention will be described through examples.
  • a step of preparing an aqueous solution of graphene oxide is performed.
  • the step of preparing an aqueous solution of graphene oxide is performed by ultrasonically dispersing 100 mL of a 0.1 wt.% aqueous solution of graphite oxide for 4 hours.
  • a step of preparing a first solution in which the first additive is dissolved in the first solvent is performed.
  • the step of preparing the first solution is performed by dissolving ethylenediamine as a first additive in a dimethylformamide (DMF) solution as a first solution.
  • DMF dimethylformamide
  • a step of preparing functionalized graphene having a functional group A is performed by mixing, stirring, and reacting the aqueous graphene oxide solution and the first solution.
  • the prepared graphene oxide aqueous solution and the first solution were mixed with each other and then reduced and reformed at 120° C. for 24 hours while stirring, thereby preparing functionalized graphene in which an amine group was formed as a functional group A.
  • the prepared functionalized graphene should be separated from the solvent and dried. After the step of preparing the functionalized graphene is finished, the functionalized graphene is separated by centrifugation under the conditions of 4000 rpm and 10 minutes. The separated functionalized graphene is placed in 1 L of distilled water and washed at 200 rpm for 1 hour. After hanging the functionalized graphene through a filter, it was dried in a vacuum oven at a temperature of 40°C for 1 hour.
  • the dried functionalized graphene is placed in a main solvent and ultrasonically dispersed to prepare a functionalized graphene colloid.
  • a functionalized graphene colloid it is preferable to use the same solvent as the solvent of the coating composition as the main solvent.
  • the synthesized functionalized graphene was again put in 100 mL of isopropyl alcohol (IPA), mixed at 10 k rpm with a homogenizer for 10 minutes, and then ultrasonically dispersed for 1 hour to prepare a first functionalized graphene colloid.
  • the first functionalized graphene colloid prepared in this step contains the functionalized graphene of the first embodiment.
  • the manufacturing method is terminated at this stage.
  • the step of preparing a second solution in which the second additive is dissolved in a second solvent is further performed.
  • 20wt% of PUD aqueous solution waterborne polyurethane dispersion
  • a second functionalized graphene colloid containing the functionalized graphene of the second embodiment was prepared by mixing 100 ml of a functionalized graphene colloid aqueous solution and 0.5 g of a 20 wt% PUD aqueous solution, and performing ultrasonic dispersion for 1 hour.
  • the non-oxidized graphene of the comparative example is BGF of Best Graphene Co., Ltd. having a lateral size of 2 um and a thickness of 3 to 5 nm, and the example is a second functionalized graphene colloid.
  • FIG. 5 as a result of XRD measurement, it can be seen that in the case of the comparative example, the interplanar distance is 3.391 to 3.423 ⁇ , which is less than 3.6 ⁇ , but in the case of the embodiment, the interplanar distance is 3.759 to 3.882 ⁇ and has an interplanar distance of 3.6 ⁇ or more.
  • Non-oxidized graphene 1 to 3, reduced graphene, and graphene oxide were products of Best Graphene Co., Ltd.
  • Functionalized graphene-1 is the first embodiment, wherein the functional group A is an ethylamine group
  • the functionalized graphene-2 is the first embodiment, wherein the functional group A is a phenylamine group, and the functional group A is longer than the functionalized graphene-1 is longer
  • functionalized graphene 3 is a second embodiment, wherein the functional group A is a phenylamine group, and the organic monomer or polymer connected to the functional group A is urethane. Meanwhile, the interplanar distance of graphene was calculated by XRD analysis and Bragg's equation (Equation 1).
  • Comparative Example 1 is a coating layer (commercial product C) formed with a coating composition for wiper blades of Company C, which is currently commercially available
  • Comparative Example 2 is a coating layer formed with a coating composition for wiper blades of Company D, which is currently commercially available (top).
  • article D is a coating layer formed of a coating composition for a wiper blade comprising functionalized graphene (functional group A-amine group) according to the first embodiment
  • Example 2 is a functionalized graphene (functional group) according to the second embodiment It is a coating layer formed of a coating composition for wiper blades including group A-amine group, functional group B-urethane group).
  • Example 2 showed the highest adhesion, and Example 1 also showed adherence. On the contrary, in Comparative Examples 1 and 2, the coating layer immediately fell from the rubber base when the 3M tape was attached and then peeled off.
  • FIG. Figure 8 (a) is an image taken with an optical microscope of the surface of the wiper blade rubber base without a coating layer
  • FIG. Figure 8 (c) is an image taken with an optical microscope of the surface of the wiper blade rubber base formed of the coating layer of the embodiment.
  • Comparative Example is a coating layer formed with a coating composition for wiper blades of Company D, which is currently commercially available, and uses graphite powder. Looking at the optical photograph of the comparative example, it can be seen that the graphite powder is fixed by a binder.
  • An example is a coating layer formed of a coating composition for a wiper blade including functionalized graphene (functional group A-amine group, functional group B-urethane group) according to the second embodiment. It can be seen that, unlike the comparative example, the functionalized graphene is continuously formed in the form of a thin sheet with a large area.
  • the friction coefficient is at least 0.26 g/cm and up to 0.43 g/cm lower than those of Comparative Examples 1 and 2 to have high lubrication performance. Comparing the first embodiment with the second embodiment, it can be seen that the first embodiment has a lower coefficient of friction, and the second embodiment has better adhesion.
  • Wiping performance was evaluated for Comparative Examples 2 and 1 to 3 in Table 4 above. Wiping performance was evaluated in the same manner as in Table 1, and the evaluation was performed according to the number of turns of the wiper.
  • Example 2 9.0 7.8 7.8 6.5 3.5
  • Example 1 10.0 8.6 8.0 7.0 6.0
  • Example 2 10.0 10.0 9.5 7.8 6.5
  • Example 3 10.0 9.0 9.0 7.5 6.2

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  • Inorganic Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

La présente invention concerne une composition de revêtement, destinée à un balai d'essuie-glace, pour former une couche de revêtement destinée à abaisser le coefficient de frottement d'une base de balai d'essuie-glace en caoutchouc par rapport au verre, la composition de revêtement comprenant un additif lubrifiant et un solvant, l'additif lubrifiant étant un graphène fonctionnalisé pouvant s'auto-coller sur une base de balai d'essuie-glace en caoutchouc.
PCT/KR2021/003893 2021-03-30 2021-03-30 Composition de revêtement de balai d'essuie-glace comprenant du graphène fonctionnalisé ayant une adhésivité améliorée au caoutchouc, et son procédé de préparation WO2022211141A1 (fr)

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KR1020237023571A KR20230121804A (ko) 2021-03-30 2021-03-30 고무에 대한 부착성이 향상된 기능화 그래핀을 포함하는와이퍼 블레이드 코팅 조성물 및 그 제조방법
US18/270,834 US20240075905A1 (en) 2021-03-30 2021-03-30 Wiper blade coating composition comprising functionalized graphene having enhanced adhesiveness to rubber, and preparation method thereof
PCT/KR2021/003893 WO2022211141A1 (fr) 2021-03-30 2021-03-30 Composition de revêtement de balai d'essuie-glace comprenant du graphène fonctionnalisé ayant une adhésivité améliorée au caoutchouc, et son procédé de préparation

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JP2020510121A (ja) * 2017-03-22 2020-04-02 クリューバー リュブリケーション ミュンヘン ソシエタス ヨーロピア ウント コンパニー コマンディートゲゼルシャフトＫｌｕｅｂｅｒ Ｌｕｂｒｉｃａｔｉｏｎ Ｍｕｅｎｃｈｅｎ ＳＥ ＆ Ｃｏ．ＫＧ グラフェン含有被膜潤滑剤
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KR20130037329A (ko) * 2011-10-06 2013-04-16 한국과학기술원 유기공액고분자를 이용한 그래핀 표면 개질 방법
KR20160140508A (ko) * 2015-05-28 2016-12-07 주식회사 동진쎄미켐 2종 이상의 아민을 포함하는 기능화 그래핀 및 그 제조방법
JP2020510121A (ja) * 2017-03-22 2020-04-02 クリューバー リュブリケーション ミュンヘン ソシエタス ヨーロピア ウント コンパニー コマンディートゲゼルシャフトＫｌｕｅｂｅｒ Ｌｕｂｒｉｃａｔｉｏｎ Ｍｕｅｎｃｈｅｎ ＳＥ ＆ Ｃｏ．ＫＧ グラフェン含有被膜潤滑剤
KR101923648B1 (ko) * 2017-11-16 2018-11-29 계명대학교 산학협력단 기능화된 산화그래핀을 이용한 유성 윤활제 제조방법
JP2020163981A (ja) * 2019-03-29 2020-10-08 バンドー化学株式会社 ワイパーラバー用コーティング剤及びワイパーラバー

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024099464A1 (fr) * 2022-11-11 2024-05-16 浙江科普特新材料有限公司 Matériau tpv auto-lubrifiant ayant un faible coefficient de frottement de glissement, son procédé de préparation, et son utilisation

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